Resinous material and method of producing



Patented June 15, 1937 UNITED STATES- PATENT OFFICE nlsmous MATERIAL mmuon' or raonucmc Arthnr L. Osterhoi', Kenvll, N. 3., a llgnor uWilmington,

Hercules Powder Company,

Del.,l

corporation of Delaware Application December I7, 1030. SerialNo. 505.207

My invention relates to an improvement in rosin products and method ofproducing. More particularly my invention relates to rosin conglensationproducts and method for their produc- In accordance with my invention, Ihave produced a rosin condensation product which may be in the form ofrosin or which may be esterifled if desired, or which may be produced asan esteriflcatiou product, depending upon the mode of procedure. Theproduct whether produced as a rosin product or as a rosin esteriflcationproduct, will be found to be of relatively high viscosity and highmelting point as compared with the rosin treated.

'I'he product will be found to behighly advantageous for use, forexample, in varnishes, lacquers, etc., etc. and, in fact, for all usesfor which rosins of higher viscosity and melting point may be desirable.Further, the product whe're produced as a rosin product will be foundadvantageous for the preparation of rosin esters of higher viscosity andmelting point, which will be found desirable for all uses for whichrosin esters are required or desirable and for which uses the productwhere produced as an esteriflcationproduct will likewise be foundadvantageous.

In the production of the product by the method in accordance with myinvention, rosin, as for example, wood or gum rosin. of any commercialgrade or alternatively commercial abietic acid, is condensed with analdehyde in the presence of an acid. The aldehyde may be formaldehyde,acetaidehyde, benmldehyde, etc., or an operable as quivalent therefor.Where condensation is effected in the presence of an organic acid, itwill be found that some of the organic acid will esterify' withalcoholic groups formed by the condensation, while where thecondensation is 40 effected in the presence of an inorganic acid,

no esterification will take place. Where the product is produced as aresin product, it may, if desired, be readily esteriiled andalternatively, where the product is produced as an ester-incationproduct, the acid condensing agent which is esteriiled with thecondensation product may be readily removed, for example, bysaponiflcation with an excess of alkali and finally freeing the resinacids with an excess of an acid, as for example, acetic, hydrochloric,etc.

In carrying out the method in accordance with my invention, it has beenfound that rosin or abietic acid may be condensed with either one or twomolecules, or even four under proper conditions, of an aldehyde, asformaldehyde, with one to sixteen hours.

treatment of abietic acid or rosin with an aidehyde or operableequivalent in the presence of an acid. The treatment, where necessary toeffect condensation, will be at an elevated temperature. For example, ashas been indicated, the aldehyde may be formaldehyde, acetaldehyde,benzaldehyde, etc.. etc. or any operable equivalent therefor. As thecondensing agent inorganic acids, as for example, hydrochloric,phosphoric, etc., etc. acids may be used or an organic acid, as forexample p-toluene sulfonic, acetic, salicylic, benzoic, phthalic,oxalic, malic, tartaric, mucic, gluconic, citric, etc., etc. may beused.

As illustrative of the practical adaptation of the method in accordancewith my. invention, for example:

1 mol. of abietic acid 2 mols of CHzO as paraformaldehyde l to 1.5 molsof acetic acid are heated under a reflux condenser or in a closed vesselat a temperature of say, for example, C.-l30" C. until the odor offormaldehyde has disappeared or, for example, from about one The productis then diluted with a suitable solvent, as for example, gasoline,benzene, toluene, alpha pinene, etc., etc., or any operable equivalenttherefor, and the excess acid is removed by washing with water or adilute alkali solution, as for example, a solution of sodium carbonate.The use of a dilute alkali solution will be found advantageous where theacid used is difllcultly soluble in water. In the case of some acids theacid may desirably be removed by distillation. After removal of theexcess acid the product is recovered by distilling oi! the solvent.

In the above illustration the product will be a rosin of increasedviscosity and melting point.-

Where an organic acid is used theproduct will be found to be esterifiedwith the acid.

Where the product is esterifled with the acid, the acid esterified withthe rosin condensation product may be removed by, for example,saponification of the rosin with an excess of alkali, as for example,caustic soda or potash and treated with an excess of an acid, as aceticacid, sulphuric acid, hydrochloric acid, or an operable equivalenttherefor, to free the resin acids. On washing with water or, wheredesirable, with dilute alkali solution, the product, as a rosincondensation prodnot of high viscosity and melting point as comparedwith the ester, will, in most cases, be obtained.

As further illustrative of the practical adaptation of the method inaccordance with my invention, for example, 1 mol of commercial abieticacid dissolved in 300 cc. of toluene, 2 mols oi CHaO as paraformaldehydeand 0.002 mol. of p-toluene 5 sulfonic acid are warmed gently to theboiling point and refluxed until the odor of formaldehyde disappers, sayfrom two to four hours.

In carrying the method in accordance with my invention into practicewhere the acid used is in solid form, it may be found desirable toutilize a small amount of solvent .tor the acid. The solvent may be anydesired solvent for the acid which will be inert to the aldehyde androsin and may, for example, be benzene, gasoline, toluene, water, etc.,etc.

The treated mixture is then further diluted if necessary, washed withwater and the solvent distilled of! to obtain rosin condensationproduct,

' which will be found to be a rosin of high viscosity and melting point.

As has been indicated, where the product is produced as a rosincondensation product as,

sation product and phthalic anhydride may be heated to a temperature oisay 150 C.-170 C. 35 for say 30 minutes. The product may then be dilutedwith a solvent immiscible with water, excess of acid washed out withwater or with a dilute alkali solution and the benzene removed for therecovery of the esteriflcation. product by distillation..

As has been indicated, in producing the product in accordance with'myinvention and in the carrying out of the method embodying my invention,abietic acid, as commercial abietic acid, may be used, or alternatively,various grades of rosin may be used, since the reaction requires onlythe presence of a reactive double bond. Further, it will be understoodthat the method in accordance with my invention is adaptable todensation products by the treatment with an aldehyde and an acidcondensing agent, as fully described above, oi a rosin or abietic acidester, as for example, glycerin ester, ethyl abietate, methyl abietate,glycol abietate, etc., etc. The ester condensation product will have ahigh viscosity and melting point relative to the ester treated and willbe similar to the esters of the esterifled .condensation productsproduced in aced with an aldehyde and an organic acid or where the rosincondensation product produced in accordance with my invention issubjected to esteriflcation.

the production of rosin or abietic acid ester con cordance with myinvention where rosin is treat It will be understood that I contemplateas I densing agent. It will also be understood that I do not contemplatemy invention as limited to the use of the aldehydes, acids, etc. morespeciflcally mentioned herein, but to the contrary that I. contemplatethe use of operable equivalents therefor. What I claim and desire toprotect by Letters Patent is:'

1. The method for producing an abietic acid product which includeseilfecting direct condensation of esteritled abietic acid with analdehyde in the presence of an acid selected from the group consistingotinorganic acids, organic carboxylic acids other than resin acids, andsultonic acids.

2. The method for producing an abietic acid product which includeseirecting direct condensation of esteritled abietic acid with analdehyde in the presence of an organic carborylic acid other than aresin acid.

3. The method for producing an abietic acid product which includeseflecting direct condensation of esteriiied abietic acid with analdehyde in the presence 01 an inorganic acid.

4. The method for producing an abietic acid product, which includesefiecting direct condensation of abietic acid with an aldehyde in thepresence of p-toluene sulionic acid.

5. The method for producing an abietic acid product, which includeseflecting direct condensation of esterifled abietic acid with analdehyde in the presence of malic acid.

6. The method for producing an abietic acid product which includeseflecting direct condensation of esteriiled abietic acid with analdehyde in the presence of hydrochloric acid.

7. The method for producing an abietic acid product, which includesefl'ecting direct condensation of esterifled abietic acid with analdehyde in the presence of p-toluene' sulionic acid.

8. The method for producing an abietic acid product which includeseffecting direct condensation of esterifled abietic acid withformaldehyde in the presence oi. malic acid.

9. The method for producing an abietic acid product, which includeseflfecting direct condensation of esterifled abietic acid withformaldehyde in the presence of hydrochloric acid.

10. The method for producing an abietic acid product, which includeseflecting direct condensation oi esterifled abietic acid withformaldehyde in the presence of p-toluene sulfcnic acid.

11. The method for producing an abietic acid product, which includeseflecting direct condensation o1 esterifled abietic acidwithformaldehyde in the presence or an acid selected from the groupconsisting of inorganic acids, organic carboxylic acids other than resinacids, and sulionicacids.

12. The method for producing an abietic acid product, which includeseflecting direct condensation of esterifled abietic acid withformaldehyde in the presence of an organic carboxylic acid other than aresin acid.

13. The method for producing an abietic acid product, which includeseffecting direct condensation oi. esterifled abietic acid withformaldehyde in the presence of an inorganic acid.

- 14; As a new composition of matter the product of the reaction 01'esterifled abietic acid with an aldehyde in the presence of a sulfonicacid.

15. As a new composition ofmatter the product or the reaction ofesterified abietlcacid with an aldehyde in the presence 01' an organiccarboxylic acid other-than a resin acid.

16. As a new composition of matter the product of the reaction ofesterifled abietic acid with an aldehyde in the presence of an inorganicacid.

17. The method for producing an abietic acid product which includeseffecting direct condensation of an abietic acid compound selectedfromthe group consisting oi abietic acid and abietic acid esters with analdehyde in the presence of i0 p-toiuene sulfonic acid. ARTHUR L.OS'I'ERHOF. 10

CERTIFICATE OF CORRECTION.

Patent No. 2,084,213. June 15 1957.

\ I ARTHUR L. OSTERH OF It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionas follows: Page 1, second column, line 18, strike out the period after"mol"; page 2, first column, line '7, for "disappers" read disappears;and second column, line 18. claim 2, for "carborylic" read carboxylic;and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 14th day-of September, A. D. 1937;

Henry Van Arsdale (Seal) Acting Commissioner of Patents.

16. As a new composition of matter the product of the reaction ofesterifled abietic acid with an aldehyde in the presence of an inorganicacid.

17. The method for producing an abietic acid product which includeseffecting direct condensation of an abietic acid compound selectedfromthe group consisting oi abietic acid and abietic acid esters with analdehyde in the presence of i0 p-toiuene sulfonic acid. ARTHUR L.OS'I'ERHOF. 10

CERTIFICATE OF CORRECTION.

Patent No. 2,084,213. June 15 1957.

\ I ARTHUR L. OSTERH OF It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionas follows: Page 1, second column, line 18, strike out the period after"mol"; page 2, first column, line '7, for "disappers" read disappears;and second column, line 18. claim 2, for "carborylic" read carboxylic;and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 14th day-of September, A. D. 1937;

Henry Van Arsdale (Seal) Acting Commissioner of Patents.

